KR20180042265A - Decorative sheet - Google Patents

Abstract

Provided is a decorative sheet comprising a transparent resin layer having excellent subsequent processability and high transparency. The decorative sheet 1 according to one embodiment of the present invention has a transparent resin layer 4 mainly composed of a crystalline polypropylene resin and the transparent resin layer 4 has a peak strength represented by the following formula (1) The value of the ratio x is x? 0.65. I997, I938 and I973 in the following formula (1) are the peak intensity values calculated from the absorption spectra obtained by the Fourier-type infrared spectroscopy of the transparent resin layer, I997 is the peak intensity value at a wavenumber of 997 cm ^-1 , I938 is a peak intensity value of the wave number 938cm ^-1, I973 denotes a peak intensity value of the wave number 973cm ^-1.

Description

Decorative sheet

The present invention relates to a decorative sheet.

As a technique relating to a decorative sheet using an olefin resin which has been attracting attention as a decorative sheet for a polyvinyl chloride decorative sheet, there is, for example, one disclosed in Patent Documents 1 to 6.

However, these decorative sheets have a problem that it is difficult to provide a transparent resin layer having excellent after-workability and high transparency.

Japanese Patent Application Laid-Open No. 2-128843 Japanese Patent Laid-Open No. 4-083664 Japanese Unexamined Patent Application Publication No. 6-001881 Japanese Unexamined Patent Application Publication No. 6-198831 Japanese Patent Application Laid-Open No. 9-328562 Japanese Patent No. 3772634

An object of the present invention is to solve such a problem and to provide a decorative sheet having a transparent resin layer having excellent after-processing property and high transparency.

In order to achieve the above object, a decorative sheet according to one aspect of the present invention has a transparent resin layer containing a crystalline polypropylene resin as a main component, and the transparent resin layer has a peak intensity ratio represented by the following formula (1) The value of x is x? 0.65. I997, I938 and I973 in the following formula (1) are the peak intensity values calculated from the absorption spectra obtained by the Fourier-type infrared spectroscopy of the transparent resin layer, I997 is the peak intensity value at a wavenumber of 997 cm ^-1 , I938 is a peak intensity value of the wave number 938cm ^-1, I973 denotes a peak intensity value of the wave number 973cm ^-1.

According to one aspect of the present invention, it is made possible to provide a decorative sheet having a transparent resin layer having excellent after-workability and high transparency.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic sectional view showing the configuration of a decorative sheet according to a first embodiment of the present invention. Fig.
2 is a schematic cross-sectional view showing the configuration of a decorative sheet according to a second embodiment of the present invention.

The decorative sheet of each embodiment of the present invention has a transparent resin layer (hereinafter also referred to as a "transparent resin sheet") containing a crystalline polypropylene resin as a main component, and the transparent resin layer is represented by the following formula (2) The value of the peak intensity ratio x is x? 0.65. I997, I938 and I973 in the following formula (2) are the peak intensity values calculated from the absorption spectra obtained by the Fourier-type infrared spectroscopy of the transparent resin layer, I997 is the peak intensity value at a wave number of 997 cm ^-1 , I938 is a peak intensity value of the wave number 938cm ^-1, I973 denotes a peak intensity value of the wave number 973cm ^-1.

The phrase " comprising a crystalline polypropylene resin as a main component " means that 80% by mass or more and 100% by mass or less, preferably 90% by mass or more and 100% by mass or less, of the resin constituting the transparent resin layer, Polypropylene resin.

It is particularly preferable that the peak intensity ratio x of the transparent resin sheet is 0.55? X? 0.65. By setting the peak intensity ratio x within the above range, it is possible to provide a decorative sheet having a transparent resin layer having extremely excellent subsequent workability.

In the decorative sheet of each embodiment of the present invention, the peak intensity value x of the transparent resin sheet is set within the above range by controlling film forming conditions as process parameters. At this time, it is preferable that the transparent resin sheet is formed to have a thickness of 20 mu m or more and 200 mu m or less. The reason for this is that it is difficult to ensure scratch resistance if it is thinner than the thickness of the above range, and if the thickness is thicker than the above range, the resin sheet is not uniformly cooled in the thickness direction. As a result, It can not be done. It is more preferable that the transparent resin layer is formed to a thickness of 30 占 퐉 or more and 150 占 퐉 or less.

[Regarding Control of Peak Intensity Ratio x]

The film forming conditions for adjusting the peak intensity ratio x within the above range may be those capable of adjusting the degree of crystallization of the polypropylene resin. In each of the embodiments of the present invention, the degree of crystallization is adjusted by adjusting the resin temperature, the cooling temperature, . By controlling one or a plurality of these conditions, the peak intensity ratio x can be set within the above range.

More specifically, the resin temperature is the temperature at which the molten resin is discharged at the time of film formation, and the peak intensity ratio x increases as the resin temperature is increased (the higher the temperature). The cooling temperature refers to a temperature at which the discharged resin is cooled, and the peak intensity ratio x increases as the cooling temperature (the higher the temperature) is. With respect to the cooling time, the peak intensity ratio x is increased by increasing the passage time of the vicinity of the crystallization temperature (100 to 130 ° C) of the polypropylene resin. By combining the above-described conditions, the crystallinity and crystallite size in the resin can be controlled to appropriately adjust the peak intensity ratio x.

[About Fourier-type infrared spectroscopy]

Hereinafter, the Fourier-type infrared spectroscopic measurement will be described.

First, the infrared spectroscopic measurement is a method of measuring infrared light by using the principle that the amount of infrared light, which is a light with a wavelength of 0.7 to 1000 탆, changes in the amount of the infrared light absorbed by the substance, It is a measurement method that obtains information on the chemical structure or state of a substance by measuring the infrared light absorbed by the substance.

In particular, a wavelength range called mid-infrared, which has a wavelength of 2.5 to 4 탆, in which a material-specific spectrum appears, is mainly used.

In a specific measuring method of the Fourier-type infrared spectroscopy, light (infrared light) emitted from a light source is incident on an interferometer through a semi-transparent mirror, and is divided into transmitted light and reflected light. The transmitted light and the reflected light are reflected by the fixed-diameter moving lens and returned to the half-diameter, and are synthesized again to be an interference wave. Since the optical path difference is different depending on the position where the moving mirror is moved, different interference waves are obtained.

These different interference waves are irradiated to the material, and the infrared spectra are measured by calculating the intensity of the light of each wave number component from the intensity of the transmitted or reflected light from the material. Particularly, in each of the embodiments of the present invention, the calculation of the interference wave was performed by using the Fourier transform method, and the measurement was performed by Fourier-type infrared spectroscopy, which is a method of measuring the infrared spectrum. The graph obtained by plotting the wavenumber obtained by the above method on the horizontal axis and the measured absorbance (or transmittance) on the vertical axis is called an infrared absorption spectrum (or infrared transmission spectrum), and a unique pattern is shown for each substance. At this time, since the value of the peak intensity at a predetermined wave number changes in proportion to the concentration or thickness of the substance or the amount of the crystalline or amorphous portion in the case of the crystalline resin, the absorbance at the vertical axis changes from the height or area of the peak It is also possible to perform analysis.

In each embodiment of the present invention, with the same characteristics as above described in the infrared absorption spectrum, which corresponds to the absorbance of poly crystalline portion of the transparent resin sheet of polypropylene in the absorption spectrum obtained by the above measurement frequency 997cm ^-1 Is calculated based on the above formula (2), that is, the ratio of the peak intensity at a wave number of 973 cm ^-1 corresponding to the absorbance of the amorphous portion of the transparent resin sheet, that is, the peak intensity ratio x indicating the degree of crystallization of polypropylene. By making clear the relationship between the peak intensity ratio x thus calculated and the scratch resistance of the transparent resin sheet and employing the transparent resin layer corresponding to the transparent resin sheet having the peak intensity ratio x within the above range, Sheet. Further, the wave number of 997cm ^-1 peak intensity of peak intensity and frequency 973cm ^-1 are respectively subjected to background correction using the peak intensity of the wave number 938cm ^-1.

[Crude nucleating agent]

Further, in the decorative sheet of each embodiment of the present invention, it is preferable that a nano-sized nucleating agent is added to the transparent resin sheet as the transparent resin layer. Particularly, it is preferable that the nano-sized nucleating agent is a nucleating agent vesicle containing a nucleating agent in a vesicle having an outer film of a single-layer film. By adding the crude nucleating agent vesicle to the polypropylene resin, the degree of crystallization of the polypropylene resin can be improved and a transparent resin sheet having extremely high transparency can be obtained.

[Production method of crude nucleating agent vesicle]

The crude nucleating agent vesicle may be prepared by supercritical reverse phase evaporation. This supercritical reversed-phase evaporation method is a method of producing a nano-sized vesicle (capsule) containing a target substance by using carbon dioxide under a temperature condition of supercritical state or above a critical point or under a pressure condition exceeding a critical point. The supercritical carbon dioxide means carbon dioxide in a supercritical state at a critical temperature (30.98 ° C) and a critical pressure (7.3773 ± 0.0030 MPa) or more. Further, carbon dioxide under a temperature condition equal to or higher than a critical point or under a pressure condition equal to or higher than a critical point means carbon dioxide under a condition that the critical temperature or the critical pressure exceeds the critical condition.

Specifically, water is injected into a mixed fluid containing carbon dioxide and phospholipid in supercritical state and a nucleating agent as an encapsulating material, and stirred to produce carbon dioxide and an aqueous emulsion of supercritical state. Thereafter, when the pressure is reduced, carbon dioxide expands and evaporates to generate a phase, and a nanobesecle is produced in which the phospholipid covers the surface of the nucleating agent nanoparticles with a single layer film. According to this supercritical reverse-phase evaporation method, a vesicle of a monolayer film can be produced, so that a vesicle of an extremely small size can be obtained.

The average particle diameter of the coagulating agent vesicle containing a nano-sized coagulating agent is preferably 1/2 or less of the visible light wavelength (400 nm to 750 nm), more specifically 200 nm to 375 nm or less. Further, in the resin composition, the outer shell of the vesicle is broken, and the nucleating agent vesicle is present in a state where the nuclide-sized nucleus agent is exposed. By making the grain size of the nucleating agent to be a very small size within the above range, it is possible to realize a transparent resin sheet having high transparency by reducing light scattering.

The crude nucleating agent is not particularly limited as long as it is a substance that is a starting point of crystallization when the resin is crystallized. Examples of the nucleating agent include phosphoric acid ester metal salt, benzoic acid metal salt, pimelic acid metal salt, rosin metal salt, benzylidene sorbitol, quinacridone, Talc, and the like. Particularly, in each embodiment of the present invention, it is preferable to use phosphate ester metal salts, benzoic acid metal salts, pimelic acid metal salts and rosin metal salts which can be expected to have transparency.

Examples of the phospholipid include glycerol phospholipids such as phosphatidylcholine, phosphatidylethanolamine, phosphatidylserine, phosphatidylserine, phosphatidylglycerol, phosphatidylinositol, cardiopine, yellow lecithin, hydrogenated yellow lecithin, soybean lecithin, hydrogenated soybean lecithin , Sphingomyelin, ceramide phosphoryl ethanolamine, ceramide phosphoryl glycerol, and the like.

[Crystalline polypropylene resin]

The crystalline polypropylene resin is not particularly limited, but a homopolymer of propylene having a pentad fraction (mmmm fraction) of 95% or more, more preferably 96% or more, that is, a homopolymer of highly crystalline homopolypropylene resin is used .

The pentad fraction (mmmm fraction) refers to the resin composition constituting the transparent resin layer by ¹³ C-NMR measurement (nuclear magnetic resonance measurement) using a carbon C (radionuclide) having a mass number of 13 at a predetermined resonance frequency (Electromagnetic wave absorptivity) obtained by resonance with the resin, and defines the atomic arrangement, the electronic structure, and the microstructure of the molecule in the resin composition. The pentad fraction of the polypropylene resin refers to the ratio of five propylene units obtained by ¹³ C-NMR and is used as a measure of crystallinity or stereoregularity. Such a pentad fraction is one of the important factors determining the scratch resistance of the surface. Basically, the higher the pentad fraction, the higher the degree of crystallization of the sheet, and hence the scratch resistance is improved.

<Composition of Facial Sheet>

Hereinafter, specific examples of the constitution of the decorative sheet according to the first embodiment and the second embodiment of the present invention will be described with reference to Figs. 1 and 2. Fig.

Here, the drawing is schematic, and the relationship between the thickness and the planar dimension, the ratio of the thickness of each layer, and the like are different from reality. In addition, for the sake of brevity, well-known structures are shown in the drawings. In the drawings, the same or similar functions are denoted by the same reference numerals, and redundant description is omitted. It should be noted that the following embodiments are illustrative of the structure for embodying the technical idea of the present invention, and the technical spirit of the present invention is not limited to the material, shape and structure of the constituent parts. Further, the technical idea of the present invention can make various changes within the technical scope defined by the claims in the claims.

(First Embodiment)

<Overall configuration>

Fig. 1 shows a configuration of a decorative sheet 1 (1a) according to a first embodiment of the present invention. The decorative sheet 1a is provided with a primer layer 6, a concealment layer 2, a pattern print layer 3, a transparent resin layer 4, and a top coating layer (not shown) from the base material B side to which the decorative sheet 1a is applied 5) are stacked in this order. Examples of the base material (B) include wood-base materials, inorganic-base materials, metal plates, and the like.

[Primer layer (6)]

The material of the primer layer 6 may be suitably selected from the group consisting of a quality screen as a binder, cellulose, vinyl chloride-vinyl acetate copolymer, polyvinyl butyral, polyurethane, acrylic, Can be selected and used. They may be in any form, including aqueous, solvent, and emulsion types. The curing method may be appropriately selected from a single-liquid type for curing alone, a two-liquid type using a curing agent in combination with a base, and a type for curing by irradiation with ultraviolet rays or electron beams. As a general curing method, a two-liquid type in which an isocyanate curing agent is added to a urethane-based curing agent is used, and this method is suitable from the viewpoints of workability, price and cohesion of the resin itself. In addition to the binder, colorants such as pigments and dyes, extender pigments, solvents, various additives, and the like are added. Particularly, in the primer layer 6, it is located on the uppermost surface of the decorative sheet 1a. Therefore, taking into consideration that the decorative sheet 1a is wound up as a continuous plastic film (web type), it is possible to prevent the occurrence of blocking such as difficulty in slipping or peeling of the films, It is necessary to increase the adhesion of the substrate. Therefore, an inorganic filler such as silica, alumina, magnesia, titanium oxide, barium sulfate or the like may be added to the primer layer 6. Since the layer thickness of the primer layer 6 is intended to ensure adhesion with the base material B, it is preferable that the thickness is in the range of 0.1 mu m to 3 mu m.

[Concealment layer (2)]

As the material of the cover layer 2, basically, a material used for the primer layer 6 can be used. However, when the hiding property is important, it is preferable to use titanium oxide, iron oxide or the like which is opaque pigment Do. It is also preferable to add metals such as gold, silver, copper and aluminum in order to further improve the hiding ability. In general, flake aluminum is often added. The cover layer 2 can be formed by using the above-mentioned materials, for example, a comma coater, a knife coater, a lip coater, a metal deposition or a sputtering method. If the layer thickness of the cover layer 2 is less than 2 mu m, the hiding ability is insufficient. If it exceeds 10 mu m, the cohesive force of the resin material as the main component is weakened.

[Printed layer (3)]

The same material as that of the primer layer 6 can be used for the material of the pattern print layer 3 as well. Examples of the highly versatile pigment include pearl pigments such as condensed azo, insoluble azo, quinacridone, isoindoline, anthraquinone, imidazolone, cobalt, phthalocyanine, carbon, titanium oxide, iron oxide and mica have. The pattern printed layer 3 can be formed on the transparent resin layer 4 by using the above-described materials by, for example, gravure printing, offset printing, screen printing, flexographic printing, electrostatic printing, have. In addition to the method of applying the ink containing the mixture of the binder and the pigment to form the pattern printed layer 3, it is also possible to apply a pattern by vapor deposition or sputtering of various metals.

[Transparent resin layer (4)]

The transparent resin layer 4 is made of a crystalline polypropylene resin as a main component (90 to 100% by weight), and if necessary, a conventional heat stabilizer, a flame retardant, an ultraviolet absorber, a photostabilizer, , A light-scattering agent, and a gloss-adjusting agent may be used as the transparent resin sheet (4). Particularly, in the decorative sheet 1a of the present embodiment, the molding process conditions are controlled so that the peak intensity ratio x calculated based on the formula (2) from the infrared absorption spectrum measured by the Fourier type infrared spectroscopic measurement is x Lt; = 0.65 is preferably used. At this time, the thickness of the transparent resin sheet 4 is set to, for example, 20 mu m to 200 mu m. Specific examples of the molding processing conditions include a melting temperature of the resin composition, a temperature condition such as an extrusion temperature and a roll temperature with respect to the film formation, transporting conditions such as a winding speed of the sheet, and the like. In this embodiment, the crystallization degree of the transparent resin sheet 4 obtained by adjusting the cooling rate at the time of film formation is controlled by controlling these temperature conditions and conveying conditions, and the peak intensity ratio x is set to x? 0.65, preferably 0.55 ? X? 0.65.

Further, the resin composition constituting the transparent resin sheet (4) contains a nucleating agent vesicle. Thereby, the degree of crystallization of the resin composition can be easily improved, and a transparent resin sheet (4) excellent in transparency can be obtained.

As the heat stabilizer, for example, phenol-based, sulfur-based, phosphorus-based, hydrazine-based and the like can be used. As the flame retardant, for example, aluminum hydroxide, magnesium hydroxide and the like can be used. As the ultraviolet absorber, for example, benzotriazole-based, benzoate-based, benzophenone-based, triazine-based or the like can be used. As the photostabilizer, for example, a hindered amine type or the like can be used.

[Top coating layer (5)]

The material of the top coating layer 5 may be appropriately selected from, for example, polyurethane, acrylic, acrylic silicone, fluorine, epoxy, vinyl, polyester, melamine, aminoalkyd and urea . The shape of the material is not particularly limited, such as an aqueous, emulsion, or solvent system. The curing method may be appropriately selected from a single-liquid type which is cured alone, a two-liquid type which uses a curing agent in combination with the subject, a type which is cured by irradiation with ultraviolet rays or electron beams, and the like. Particularly, it is preferable to mix and cure an isocyanate-based curing agent with respect to a urethane-based subject from the viewpoints of workability, cost, and cohesion of the resin itself.

[Film forming method of transparent resin sheet (4)

Hereinafter, the detailed film forming flow of the transparent resin sheet 4 will be described. First, pellets of a resin composition to which various conventional additives are added are introduced into a crystalline polypropylene resin as a main component into a melt extruder as described above. Thereafter, the pellets are melted in a liquid state by heating while being heated, and the liquid resin composition is extruded from the T die provided in the extrusion port toward a cooling roll provided on the downstream side to a predetermined width. At this time, the liquid resin composition extruded from the T-die is allowed to proceed to crystallization until it reaches the cooling roll, and contact with the cooling roll to complete the crystallization. The cooling roll is rotated at a predetermined rotation speed around the central axis of the roll, and the resin composition in contact with the cooling roll becomes a sheet-shaped transparent resin sheet 4, and is conveyed downstream at a predetermined conveying speed, Is wound on a winding roll. In the present embodiment, in order to set the peak intensity ratio x of the obtained transparent resin sheet 4 within a predetermined range, the temperature of the resin composition extruded from the melt extruder as the film forming condition, the temperature of the cooling roll, .

[Method of producing the decorative sheet (1a)] [

The decorative sheet 1a of the present embodiment is obtained by applying the above material to the one side of the transparent resin sheet 4 formed by the film-forming flow by the above-described method using the pattern print layer 3, the cover layer 2, And the layer 6 are stacked in this order. In the case of forming the embossed pattern 4a in the transparent resin layer 4, the transparent resin sheet 4 is pressed using the embossing mold roll to form the embossed pattern 4a ). Further, a top coating layer 5 is formed on the surface of the embossed shape 4a to obtain a decorative sheet 1a.

In the decorative sheet 1a of the present embodiment, the thickness of the primer layer 6 is from 0.1 m to 3.0 m, the cover layer 2 is from 2 m to 10 m, the pattern printed layer 3 is from 3 m to 20 m, It is preferable that the thickness of the transparent resin sheet 4 as the resin layer 4 is 20 占 퐉 to 200 占 퐉 and that of the topcoat layer 5 is 3 占 퐉 to 20 占 퐉 and the total thickness of the decorative sheet 1a is 30 占 퐉 to 250 占 퐉 Is preferably within the range of.

(Second Embodiment)

<Overall configuration>

Fig. 2 shows the structure of the decorative sheet 1 (1b) according to the second embodiment of the present invention. The construction of the decorative sheet 1b is such that the primer layer 6, the monolayer 7, the pattern printed layer 3, the adhesive layer 8, the transparent layer 7, A ground layer 4 and a top coating layer 5 are laminated in this order. Examples of the base material (B) include wood-base materials, inorganic-base materials, metal plates, and the like.

The primer layer 6, the pattern print layer 3, the transparent resin layer 4 and the top coating layer 5 may be the same as those of the first embodiment. Therefore, the description of each layer is omitted here.

[Monogram (7)]

The monolayer 7 is a sheet-like member. As the monolayer 7, for example, paper such as a thin paper sheet, a titanium paper sheet, a resin-impregnated paper sheet, a polyethylene, a polypropylene, a polybutylene, a polystyrene, a polycarbonate , Synthetic resins such as polyester, polyamide, ethylene-vinyl acetate polymer, polyvinyl alcohol, and acrylic, or foams of these synthetic resins, ethylene-propylene polymer rubber, ethylene-propylene-diene copolymer rubber, styrene- Styrene-isoprene-styrene block copolymer rubber, rubber such as polyurethane, organic or inorganic nonwoven fabric, synthetic paper, metal foil such as aluminum, iron, gold, silver and the like. In the case of using the fabric resin sheet 7 mainly composed of a polyolefin-based resin as the monolayer 7, its surface is inactive. For this reason, it is preferable that the both surfaces of the fabric resin sheet 7 are subjected to surface activation treatment, for example, by corona treatment, plasma treatment, ozone treatment, electron beam treatment, ultraviolet ray treatment, or dichromic acid treatment. Further, the primer layer 6 may be formed between the fabric resin sheet 7 and the pattern print layer 3 in order to secure sufficient adhesion. When it is desired to conceal the decorative sheet 1b, the hiding layer 2 may be formed, or opaque pigment may be added to the fabric resin sheet 7 itself to provide hiding properties.

[Adhesive Layer (8)]

As the adhesive layer 8, for example, acrylic type, polyester type, polyurethane type and the like can be selected and used. Generally, a two-liquid type material having a urethane-based polyol as a base and an isocyanate as a hardener is used from workability, price and high cohesion.

[Method for producing the decorative sheet (1b)

The decorative sheet 1b of the present embodiment is obtained by corona treatment on both sides of the raw fabric resin sheet 7 as the raw monolayer 7 and forming a primer layer 6 on one side of the raw fabric resin sheet 7 And the pattern printed layer 3 is formed on the other side. The transparent resin sheet 4 as the transparent resin layer 4 formed by the film forming flow and the pattern print layer 3 of the fabric resin sheet 7 having the pattern print layer 3 and the primer layer 6 are formed, Are adhered and laminated by a method of applying heat pressure, for example, an extrusion laminating method or a dry laminating method, with the adhesive layer (8) interposed therebetween. Thus, a laminated film is formed. At this time, in the case of forming the embossed pattern 4a on the surface of the transparent resin layer 4, the embossed pattern 4a is formed by the method of heat pressure or the method of using the cooling roll with the unevenness, Is formed. Finally, the top coat layer 5 is laminated on the surface of the transparent resin layer 4 of the laminated film to obtain a decorative sheet 1b.

In the decorative sheet 1b of the present embodiment, the monolayer 7 has a thickness of 100 to 250 占 퐉 in consideration of printing workability and cost, an adhesive layer 8 of 1 占 퐉 to 20 占 퐉, a transparent resin layer 4 And the total thickness of the decorative sheet 1b is preferably in the range of 130 to 500 占 퐉. The thickness of the topcoat layer 5 is preferably 3 占 퐉 to 20 占 퐉.

(Effects of each embodiment)

(1) The decorative sheet (1) of each embodiment of the present invention is characterized in that the transparent resin sheet (4) as the transparent resin layer (4) comprises a crystalline polypropylene resin as a main component and, in the Fourier type infrared spectroscopy From the obtained absorption spectrum, the value of the peak intensity ratio x calculated based on the formula (2) is set in the range of x? 0.65, more preferably in the range of 0.55? X? 0.65.

According to this constitution, it is possible to provide the decorative sheet 1 having the transparent resin layer 4 excellent in subsequent workability as compared with the conventional decorative sheet.

(2) Further, the decorative sheet 1 of each embodiment of the present invention is a decorative sheet of a transparent resin sheet (4), in which a resin composition constituting a transparent resin sheet (4) A nucleating agent vesicle containing a nucleophilic agent in the syllable is added.

According to this constitution, the high dispersibility of the nucleating agent in the resin composition can be realized, and the degree of crystallization of the resin composition can be improved by the nucleating agent. Therefore, the decorative sheet 1 having the transparent resin layer 4 having extremely high transparency as compared with the conventional decorative sheet can be provided.

[Example]

Hereinafter, specific examples of the decorative sheet 1 according to the embodiment of the present invention will be described.

&Lt; Examples 1 to 4, Comparative Examples 1 to 4 >

In Examples 1 to 4 and Comparative Examples 1 to 4, 500PPM of a hindered phenol-based antioxidant (Irganox 1010, manufactured by BASF) and 100PM of a benzotriazole-based ultraviolet absorber (Tinuvin 328 , 2000PPM of a hindered amine light stabilizer (Chimassob 944, manufactured by BASF) and 1000PPM of a phosphate ester metal salt nucleating agent (Adekastab NA-21, manufactured by ADEKA) were added to a melt extruder Was used to perform the film-forming flow. Thus, a transparent resin sheet 4 having a thickness of 100 占 퐉 to be used as the transparent resin layer 4 was formed.

Table 1 shows the peak intensity ratios of the respective transparent resin sheets (4) measured for the respective transparent resin sheets (4) obtained in Examples 1 to 4 and Comparative Examples 1 to 4 thus obtained. In Examples 1 to 4 and Comparative Examples 1 to 4, the peak intensity ratio x was adjusted by controlling the extrusion temperature, the roll temperature and the sheet conveying speed at the time of film formation.

&Lt; Examples 5 and 6 >

In Examples 5 and 6, 500PPM of a hindered phenol-based antioxidant (Irganox 1010, manufactured by BASF), 2000PPM of a benzotriazole-based ultraviolet absorber (TINUVIN 328, manufactured by BASF) were added to the highly crystalline homopolypropylene resin , 2000PPM of a hindered amine light stabilizer (Chima Sov 944, manufactured by BASF), and 1000PPM of a nucleating agent vesicle 1000PM were added to the above-mentioned film-forming flow using a melt extruder. Thus, a transparent resin sheet 4 having a thickness of 100 占 퐉 to be used as the transparent resin layer 4 was formed.

Table 1 shows the peak intensity ratio x of each transparent resin sheet (4) measured for each transparent resin sheet (4) obtained in Examples 5 and 6 thus obtained. In Examples 5 and 6, the peak intensity ratio x was adjusted by controlling the extrusion temperature at the time of film formation, the roll temperature, and the sheet conveying speed.

Further, 100 parts by weight of methanol, 82 parts by weight of phosphate ester metal salt type nucleating agent (Adekastab NA-21, manufactured by ADEKA) and 5 parts by weight of phosphatidylcholine were placed in a high-pressure stainless steel container maintained at 60 캜 The mixture was stirred and mixed vigorously while 100 parts by weight of ion exchange water was injected. The mixture was stirred for 15 minutes while maintaining the temperature and pressure in the vessel, Carbon dioxide was discharged and returned to the atmospheric pressure to obtain a crude nucleating agent vesicle containing a phosphoric acid ester metal salt-based nucleating agent in vesicles having an outer membrane of the single-layer membrane. The particle diameter of the crude nucleating agent vesicle obtained was in the range of 0.05 탆 to 0.8 탆.

Corona treatment was then applied to both surfaces of each transparent resin sheet 4 of Examples 1 to 6 and Comparative Examples 1 to 4 obtained by the above method to make the surface wetting to be 40 dyn / cm or more. Further, pattern printing is performed on one surface of the transparent resin sheet 4 with a two-liquid curing type urethane ink (V180, Toyo Ink Kogyo K.K.) to form a pattern print layer 3, (V180, available from Toyo Ink Seisakusho Co., Ltd.) was applied at a coverage of 6 g / m &lt; 2 &gt; to form a concealing layer (2). The primer layer 6 was formed by applying a two-liquid curable urethane ink (PET-E, manufactured by Dainichiseika) under the application amount of 1 g / m &lt; 2 &gt; Thereafter, the other surface of the transparent resin sheet 4 was pressed using an embossing mold roll to cover the embossed pattern 4a. A two-liquid curing type urethane top coat (W184, manufactured by DIC Graphics Co., Ltd.) was applied to the surface of the embossed pattern 4a formed in this way at a coating amount of 3 g / m 2 to obtain a decorative sheet 1 having a total thickness of 110 탆, .

<Evaluation>

The V-groove bending workability test and the haze value measurement test were carried out on the decorative sheet (1) obtained in the above Examples 1 to 6 and Comparative Examples 1 to 4 to evaluate the post-processability thereof.

Hereinafter, a detailed method of each test will be described.

&Lt; V-groove bending workability test >

First, each of the decorative sheets (1) of Examples 1 to 6 and Comparative Examples 1 to 4 obtained by the above method was affixed to one side of a heavy fiber board (MDF) as the substrate (B) using a urethane adhesive, The V-shaped groove is inserted to the boundary where the base material B and the decorative sheet 1 are bonded to the other surface of the base material B so that the decorative sheet 1 on the opposite side is not scratched. Subsequently, the base material B is bent up to 90 degrees along the V-shaped groove so that the face of the face sheet 1 is folded at a mountain fold, so that whitening, cracks, and the like do not occur in the bent portion of the surface of the face sheet 1 Is observed using an optical microscope, and the evaluation of the superiority of the post-processability is carried out. The evaluation was carried out in the following two steps.

○: No whitening or cracks are observed

X: white sheet which can not be tolerated as a decorative sheet, cracks are visible

<Haze value measurement test>

Here, the haze value is a value obtained by subtracting, from all the integrated values (total light transmittance) of the light beams emitted from the other surface, light incident from one surface of the object to light emitted from the other surface, (Diffusion transmittance) obtained by subtracting the integral value (linear transmittance) of only the component (diffusion transmittance) by the total light transmittance as a percentage. The smaller the value, the higher the transparency. The haze value is determined based on the internal haze determined by the internal state of the object such as the degree of crystallization and the moon size in the crystal portion and the external haze determined by the state of the surface of the object such as the presence or absence of irregularities on the incident surface and the emitting surface It is determined by Hayes. In this test, when simply referred to as a haze value, it means a value determined by an internal haze and an external haze. This test was carried out for each transparent resin sheet 4 using a haze value measuring tester (NDH2000 manufactured by Nippon Denshoku Co., Ltd.). Blank measurement is carried out in advance without installing anything in the sample holder. In the measurement of each transparent resin sheet 4, a sample was placed in a sample holder and sample permeation measurement was carried out under the same conditions as the blank measurement, and the ratio of the sample transmission measurement and the blank measurement expressed as a percentage was calculated as a haze value. In this test, it was judged that the sample having a haze value of less than 15% was acceptable.

Table 1 shows the results of the V-groove bending workability test and the haze value measurement test.

The results of each test of each decorative sheet 1 were as shown in Table 1. The decorative sheet 1 of Examples 1 to 6, in which the peak intensity ratio x of the transparent resin sheet 4 was 0.55? X? And the cosmetic sheet (1) of Comparative Example 2 with x = 0.53 were found not to be whitened, cracked or the like in the V-groove bending workability test and had excellent after-workability. Also, for Comparative Example 1 in which the peak intensity ratio x was less than 0.53, film formation was impossible. As to the decorative sheet (1) of Comparative Examples 3 and 4, where the peak intensity ratio x was x &gt; 0.65, unacceptable whitening and cracks were seen as decorative sheets.

The haze value was 15% or less in any of Examples 1 to 6 and Comparative Examples 2 to 4, and had transparency suitable for the decorative sheet 1. Particularly, in the decorative sheet (1) of Examples 5 and 6 to which a nucleating agent vesicle was added, the haze value was smaller than that of the decorative sheet (1) of Comparative Examples 1 and 2 which had the same peak intensity ratio x Value, and it can be seen that it has better transparency. This is considered to be because scattering of light is reduced and transparency is improved because the dispersibility of the nucleating agent added to the resin composition is improved.

From the above results, it was found that when the peak intensity ratio x of the transparent resin sheet 4 as the transparent resin layer 4 is x? 0.65, and preferably 0.55? X? 0.65, the decorative sheet 1 having excellent after- It was found that

In the "judgment" column of Table 1, "excellent" shows excellent after-workability and transparency, "∘" indicates excellent after-workability and transparency, "◯" indicates excellent after-workability and transparency, have.

Further, by adding the coarse nucleating agent vesicle to the transparent resin sheet 4, the dispersibility of the nucleating agent in the transparent resin sheet 4 can be improved, and the decorative sheet 1 having extremely high transparency and excellent designability can be obtained, It was found that

The decorative sheet 1 of the present invention is not limited to the above-described embodiment and examples, and various modifications are possible within the scope of not damaging the features of the invention.

[Reference Example]

Hereinafter, a decorative sheet other than the decorative sheet described in the present embodiment will be briefly described as a reference example of the present invention.

In recent years, as described in Patent Documents 1 to 5, a number of decorative sheets using an olefin resin have been proposed as a decorative sheet instead of a polyvinyl chloride decorative sheet.

However, since these decorative sheets do not use a vinyl chloride resin, the generation of toxic gas or the like at the time of incineration is suppressed. However, since a general polypropylene sheet or a flexible polypropylene sheet is used, the scratch resistance of the surface is poor and much lower than the scratch resistance of a conventional polyvinyl chloride toilet sheet.

To solve these drawbacks, the present inventors have proposed a decorative sheet having excellent scratch resistance and subsequent workability of the surface described in Patent Document 6. However, the use of such a decorative sheet using such a decorative sheet is gradually expanding, and the awareness of the quality of the consumer is also increasingly advanced.

In general, a crystalline resin such as a polypropylene resin can change the mechanical properties by controlling the degree of crystallization which is not a ratio between the crystalline component and the amorphous component in the resin. Factors for controlling the degree of crystallization include process parameters such as a material factor by the molecular structure of the resin itself, the addition of a nucleating agent, and molding processing conditions when the crystalline resin is processed. The inventors of the present invention have focused on this process factor and have conducted intensive research and have completed the production of a decorative sheet having a resin sheet having a specified degree of crystallinity with excellent post-processability by controlling the process parameters.

In general, the crystal size of the crystalline portion of the polypropylene resin is larger than the wavelength of visible light (400 to 750 nm), so that scattering of light is increased and milky white is exhibited. However, the transparent resin layer It is necessary that the pattern or shape formed on the lower layer thereof should be seen to be clear through the transparent resin layer, and high transparency is demanded from the viewpoint of designability.

1: Facial sheet
1a: Facial sheet
1b: Facial sheet
2:
3: Printed layer
4: Transparent resin layer (transparent resin sheet)
4a: embossed shape
5: top coating layer
6: Primer layer
7: Single layer (fabric resin sheet)
8: Adhesive layer

Claims (4)

And a transparent resin layer containing a crystalline polypropylene resin as a main component,
Wherein the transparent resin layer has a peak intensity ratio x of x? 0.65 as represented by the following formula (1).
I997, I938 and I973 in the following formula (1) are the peak intensity values calculated from the absorption spectra obtained by the Fourier-type infrared spectroscopy of the transparent resin layer, I997 is the peak intensity value at a wavenumber of 997 cm ^-1 , I938 is a peak intensity value of the wave number 938cm ^-1, I973 denotes a peak intensity value of the wave number 973cm ^-1.

The decorative sheet according to claim 1, wherein the peak intensity ratio x is 0.55? X? 0.65. The decorative sheet according to claim 1 or 2, wherein the transparent resin layer contains a nano-sized nucleating agent. 4. The decorative sheet according to claim 3, wherein the nano-sized nucleating agent is contained in the transparent resin layer in a state in which the nucleating agent is contained in the vesicle having the outer film of the single-layer film.

Images